Deuterium Isotope Effects on Acid-Base Equilibrium of Organic Compounds

Deuterium isotope effects on acid–base equilibrium have been investigated using a combined path integral and free-energy perturbation simulation method. To understand the origin of the linear free-energy relationship of ΔpKa=pKaD2O−pKaH2O versus pKaH2O, we examined two theoretical models for computing the deuterium isotope effects. In Model 1, only the intrinsic isotope exchange effect of the acid itself in water was included by replacing the titratable protons with deuterons. Here, the dominant contribution is due to the difference in zero-point energy between the two isotopologues. In Model 2, the medium isotope effects are considered, in which the free energy change as a result of replacing H2O by D2O in solute–solvent hydrogen-bonding complexes is determined. Although the average ΔpKa change from Model 1 was found to be in reasonable agreement with the experimental average result, the pKaH2O dependence of the solvent isotope effects is absent. A linear free-energy relationship is obtained by including the medium effect in Model 2, and the main factor is due to solvent isotope effects in the anion–water complexes. The present study highlights the significant roles of both the intrinsic isotope exchange effect and the medium solvent isotope effect.

A Spectroscopic Overview of Intramolecular Hydrogen Bonds of NH…O,S,N Type

Intramolecular NH…O,S,N interactions in non-tautomeric systems are reviewed in a broad range of compounds covering a variety of NH donors and hydrogen bond acceptors. 1H chemical shifts of NH donors are good tools to study intramolecular hydrogen bonding. However in some cases they have to be corrected for ring current effects. Deuterium isotope effects on 13C and 15N chemical shifts and primary isotope effects are usually used to judge the strength of hydrogen bonds. Primary isotope effects are investigated in a new range of magnitudes. Isotope ratios of NH stretching frequencies, νNH/ND, are revisited. Hydrogen bond energies are reviewed and two-bond deuterium isotope effects on 13C chemical shifts are investigated as a possible means of estimating hydrogen bond energies.

Third dissociation constant of phosphoric acid in H2O and D2O from 75 to 300 °C at p = 20.4 MPa using Raman spectroscopy and a titanium-sapphire flow cell

The first reported Raman spectra and ionization constants for the phosphate ion in H2O and D2O above 50 °C quantify deuterium isotope effects under hydrothermal conditions.

Long range deuterium isotope effects on 13C NMR chemical shifts of 2-alkanones in CD3OD solutions of imidazolium acetate ionic liquids

Long range deuterium isotope effects on the carbon spectral pattern in 2-hexanone reveal the existence and distribution of H/D isotopomers.

Deuterium isotope effects on 17O nuclear shielding in a single water molecule from NMR gas phase measurements

The 17O NMR shielding constants of the isolated molecules: H2O, HOD and D2O were measured in the gas phase; the isotope effects were established and small nonadditivity was stated.